DE1704444A1 - Composite bodies that can be deformed to form molded bodies based on thermosetting compounds - Google Patents

Description

I> R. USE RUCH

MTINTANWALT MONCHENf ITA //// KöcHENÄACHsnt ti 17 U 4 4 4 η

ti

TH.

PoXlo A / 11786

Allied Chtffiloal Corporation, Hew York, M.Y., OSA

Can be deformed into molded bodies · Composite bodies based on thermosetting compounds

The invention relates to deformable bodies Composite body made of a middle layer made of an essentially uncured, thermosetting material and rare on both of which at least one layer made of a thermoplastic plastic bottle ..

The invention further provides a process sur producing Forakörpern which thereby applies gekeimse lohnet 1st "which one rteten on both Rarely a Hittellage from a wtraehärtenden" nloht-outgoing & Harsaasse a · TSM · ** ■ elnea thereoplastisohen plastic, the composite thus obtained, who is sufficiently stiff "utters the form" that is given to him, so he keeps a body

109821/1898

8AD ORIGINAL

deformed the desired porn and then the thermosetting resin at a temperature below the heat deformation temperature de · thermoplastic polymer hardens.

During the deformation of thermoplastic plastic films the relatively turf feasible for dl · deformation can apply the usual methods of sheet metal »is the one at Thermosetting plastics are not possible, and this is mainly because these tubing hard-ending plastics The physical properties required for this are missing. For example, these plastics have «before they hardened out are not the required strength, let sloh nioht stretch and fail to retain the form given to them. Therefore, moldings had to be made of thermosetting

heated plastics are kept for a considerable time in the / Ϋοπη, so that they kept their fora permanently, even after the was removed from the outer boundary prescribed by the Fox.

According to the method of the invention can now be proportionate rasoh at normal temperatures molded body on the base thermosetting Kunatoffaassen, which are hardened outside the unwieldy fons keep their shape « will.

109821/189 «

BAU OU) GiHAL

The invention is intended to be described in more detail below with reference to the drawings explained:

FIG. 1 shows a composite body according to the invention.

Figure 2 illustrates a further composite body according to the invention.

Figure 2 illustrates another modification of a Composite body of the invention.

Figures 4a to Io illustrate the ones in a similar manner Stages of a deep vision process for the production of Forum bodies equip the invention.

Figures 5a and 5b illustrate the individual stages of a alternative deformation method using " the composite of the invention. I.

Figure 6 also illustrates alternative implementations shaping the method of the invention for manufacture of molded bodies.

FIG. 7 illustrates a further Durohuhrungungformn of the method for producing the composite bodies according to the invention.

1096-21 / 1898

Until now, mold bodies had to be made from tub-hardening Resin the body almost completely raw to the limit Curing in the hot form. OenttS one such known processes are, for example, bars,

Reinforcement material, filler, pigment, etc. to a horizontal

The like mass is mixed, and this mass is then hollowed out introduced into a die and deformed and cured at suitable pressures and temperatures. Then the form body removed from the mold and reworked. Alternatively can a liquid, heat-hardening Haranasse in a form poured and using wime and pressure su de · desired Bodies are deformed and hardened.

knots It is well known that wax-hardening plastics can partially

will,
or hardened, or their viscosity can be "increased" in other ways "for example by using certain catalyst combinations" of thixotropic agents or fillers "so that they acquire a putty-like or waxy consistency; they can then be deformed and cured using pressure and elevated temperature. However, after their deformation, these semi-solid masses must also be kept in their shape until the port body has hardened.

The present invention is now sewing on the discovery « the crosslinkable polymer and crosslinkable polymer in

10 9 8-21 / 1898
BATH ORIGINAL

Connection to a sales or reinforcement material In the form of fasting, putty-like masses, impregnated family materials etc. by methods such as those used for the production of shaped bodies from sheet metal, with normal

every side

Temperatures can be deformed »'if you are on a central position a folio made of one material from this material worthwhile ductility, for example a theraoplaatiaohen Material that applies »i.e. through the two thermoplastic Pollen becomes the composite body one for the process of Er- ™ finding sufficient Porrast from i lit Ht awarded. The two thermoplastic films can be made from the same plastic or consist of different plastics.

The curing of the middle layer of the deformed composite body gearite dor invention can in the usual way, for example through the use of hardening catalysts and bsw. or Accelerator «in the heat-shrinkable mass, VHree and or or Radiation «ultraviolet light, ultrasound etc. are carried out · | ZweokaKSlg are thermoplastics and the heat-hardening plastic chosen so that the two Deokfollen be tied to the middle layer during endurance. Since there are many different usable thermoplastics and just as many different · «» would be jUtend »plastics there, composite bodies can get old Properties varying in a wide range getting produced. Those made from the composites of the invention

10 ** 21/189 *

1704U4

Shaped bodies produced are of particular interest as components.

The composite body shown in Figure 1 consists of a Middle layer 15 made of a heat-curing material and two layers 16 and 17 made of a thermoplastic material. The two outer layers can be attached to the Orenzfläohen 18 and 19 with the Be glued in the middle layer. In general, however, the curing of the middle lay-up will sufficiently bond the three Layers achieved against each other.

The composite curve shown in FIG. 2 consisting of the middle layer 20 made of a heat-reinforced material and two support layers 21 and 22 made of thermoplastic material differs from the one shown in FIG. 1 because three layers are glued together at 23 and 24 before deformation.

The composite body shown in FIG. 3 has, in addition to the middle layer 25 made of a powdered material and the two layers 26 and 28 made of thermoplastic material, a fourth layer 27. This layer can serve various purposes, for example a decorative film, a film made of electrically conductive material, etc. It can, as shown, be arranged along with the middle layer 25 and the Beok film 26, or it can also be applied to the deodorant roll 26.

109821/1191

ORIGINAL

^ ' ^H

170U44

Number and degree of wetting of those applied to the central layer Foils vary according to requirements and intended use, provided that only the outer filaments are thermoplastic and the Composite body after Miner deformation and hardening gives the middle layer sufficient dimensional stability · *.

Figures 4a to 4o illustrate the deformation βinea Composite body x 30 according to the invention. As shown in Figure 4a

shows, the composite body 30 is placed on the matrix x 32. The clamping ring 34 becomes resilient under suitable pressure pressed onto the composite body 30, as shown in FIG. 4b, and the steepel 31 is lowered under pressure, so that the Composite body 30 dl normal shape obtained, as in FIG. 4c shown. The device is usually based on this » (! • the used. The stamp 31 is set so that that it enters as far as the deepest deep Ut dl cavity 33. The dl · opening of the die 3t has an unavailable ring 34 is pressed onto the composite body with sufficient pressure, |

that a practically wrinkle-free and loher-free molded body can be generated. If this pressure is too great, the composite body may tear instead of into the Hollow out of the die "flows *" during application insufficient pressure at the periphery of the composite body Can form wrinkles. Corresponding statements are included a deep-drawing device in which the ring instead of a constant pressure set to a constant margin

1098-21 / 1898

SAO ORiGlNAL

is going to hire. The form cycle can be "pierced" (push through) with no hand on the (not shown) Leaves a fitting, similar to deforming sheet metal by deep drawing.

A die with a more complicated surface design than that shown in FIG. 4 can also be used. Such a matrix is illustrated in Figures 5a and 5b. The composite body 35 is placed over the cavity 36 of the mat and then the clamping ring is held on the holder 38. A punch 39 *, the underside of which has the shape shown at 40, which corresponds to the bottom surface 41 of the die, is lowered under pressure into the cavity so that the composite body is pressed into the shape corresponding to the shape, as shown in FIG. 5b.

FIG. 6 illustrates a continuous process for producing a composite body according to the invention and for deforming the composite body and curing the molded body. A glass fiber web 41 is pulled off the supply roller 40 and guided over carrier rollers 43 and a guide roller into ύ & η trough 42 », which contains a polyester liquid. The solution of the polyether compound is chosen so that this compound has the desired viscosity and curing takes place at the desired point in time, ie not before the composite body has been prepared to the desired shape.

1098-21 / 1898

^ v: ν ^ ^r - ^] $ AD ORIGINAL

Slides can be belaplelawaiaa by using a first at increased temperature takes place on the developing catalyst. A basic example of this is given in Example 14.

46 can run duroh dia Polyesternaaae into the trough 42 aiaafaaerbahn slide on a over the orphan 43, 43 ¹ and 45 circulating endless conveyor belt, which has the advantage, da * sla less easily serf all or can zerrelten.

With the exit of the Olasfasarbahn from the «trough 48, excess polyester can be removed by dia se 73 suaaeaen bit of your« ordered orphan 43. With a “large couple of orphans 44 are made of thermoplastic material 48 from the storage whale 47 our formation of the composite body 49 firmly attached to the middle layer. The ratio of the dloka in the middle lies 41 to the eedloks in the outer positions, if swaeJoslMlg is about UlO to 10il and preferably H4 to 2tl, Jedooh can also be outside these ranges.

The composite body 49 can, if desired, still wipe two more orphans 50 are carried out. These orphans 50 can be heavily thrown pressure forces, but not Jedooh May be so hot that the hardening of the polyetene mass is initiated. From there, the composite body can be directly

1098-21 / 1898

.... , 8ADORiQlNAI ₁ .

- ίο -

fed to a continuously operating molding device be «or it can be cut to individual blanks and packed for transport, or it can be a deformation, as in Figures 4 and 5 and in the next stage Fig. 6 illustrates 1st, subject to flocking. After the production of moldings from the composite body this molded body is removed from the cavity 61 of the die, which is shown, for example, with the one shown in FIG. 6 Transmission device 52 can be done. This transmission device can with a spring 53 »which presses the molded body out of the matrix 60, susamnenarbeltea. The moldings can then be placed on a conveyor belt 55, and this Conveyor belt can lead them through an oven 56 where they harden will. After that, they can be subjected to post-processing if desired. The deformation device shown in FIG corresponds to figure 4 shown. It has a die 60 with a cavity 61, a Hold ring 62 and a stamp 63 open.

The trough 42 is made from a mixing chamber 84 via a line 59 covered with polyester mat. From a storage container 80 is polyester via a metering device 82 and from a Container 81 catalyst via a metering device 03 in a mixing chamber 84 out of which the Gemlsoh duroh Line 59 enters trough 42.

10 9 8-21 / 1898

Alternatively, dlt woven or aioht-woven aias fiber seatte 41, as shown in Figure 6 by the dashed lines 70, guided on a straight path over the rollers 43 and file Thermosetting dimensions 51 from the extruder 86 through the nozzle 71 be applied to it. The viscosity of the mass is in such a way that they all do not drip through web 70 but are carried away by it. Duroh the powers 73 and 43 the viscous mass is then pressed into the Olasfaserbahn. *

Figure 7 veranaohaulloht another DurohftlhruagBfona de Process of the invention, wherein the central layer is water-hardening Material directly on a foil from theraoplaatiechea Material is applied, where the wide sheet of thermoplastic material is applied to the middle layer will. WKn-hardening plastic and catalyst come off the reservoir «80 and 81 via pumps 82, etc. $ 3 in one Mixing chamber 84, into which a container 85 neon a |

Reinforcement material, such as oil chamfer material, introduced can be. The one formed in the Misohkaeeei * Θ4 Oenlsoh is, for example through the extruder 86, with the nozzle 71 on the film 89 made of thermoplastic material, the is withdrawn from the roller 88 »applied. A second sheet of thermoplastic material 90 is released from the roller sucked off and applied to the heat-resistant compound 87.

109 821/1898

sxamo <**

by guiding the layers through the gap between the orphans 92 , the uniformity of the dloke of the composite body can be improved by guiding this nooa "iiiiohen ewei walxen 9 ^ hindu. The connector can then be deformed and the molded bodies can be transported away or stored as desired.

PSs ffKnnsb & rtbar · middle layer »of the composite body of the invention preferably contains a reinforcing material such as oil fiber in the form «klelntrt @ r StrMnge, and bxw. or one non-woven or interwoven Olasfaserbahn, a ·· textile fabric »« of a metal net ··, of asbestos fibers «to. Which · TeοanIk is used to manufacture the composite body, depends on the reinforcement material used and the Consistency of the removable mass. If this one high YiskoaitXt and the reinforcement material is in the course of the day, dl · components are advantageous in a Knead "a * ohlfie wrongly and directly on the surface of the under «» film made of thermoplastic · «material extruded.

Becomes a baim from the reinforcement or promotion theater used * so the heat transfer * and · plastic in one Solvents in solution or, if pre-curing agent, with sugar-smeared Virkungp such as magnesium oxide, can be used that Plastic directly by dipping or spraying onto the

1098-21 / 1898

Web can be applied from the reinforcement material. As

mentioned, the outer layers are made of thermoplastic material

a) the composite body has the desired surface properties confer, b) the composite body on the one hand the required

Strength and, on the other hand, that required for deformation Give ductility and o) the middle layer in front of, during and

limit after deformation until hardening, so that they

It retains its given shape until it is gelled. While a

After hardening, the outer layers become so firmly attached to the inner layer bound so that a one-piece molded body is formed.

I.e. in the finished molded body the hardened agent solidifies *

position the thermoplastic outer position, and the dimensional stability of the finished body is largely due to the strength of the hardened middle layer.

The fixed connection is made of thermoplastic rings

and the middle layer in the finished molded body is essential »

so that the body even at temperatures above the Olaaüber- I

running temperature of the top material a good one

Has dimensional stability.

As heat-retaining plastics for the middle layer, for example Polyesters, substituted polyesters, for example chlorinated polyesters, phenolic resins, polyurethanes,

1098-21 / 1898

BATH ORIGINAL

170UU

- 14 -

Melamine resins, epoxy resins: urea resins * Silicones and the like. be used. These plastics can be modified for example by taan they old for example thermoplastics such as polyvinyl chloride, poly-ethylene, Polystyrene and the like. You can also, as mentioned, fillers, reinforcing agents, thixotropic agents and the like, and they may be prepolymerized or precondensed or be thickened. The middle layer preferably contains an epoxy resin, a polyester or a polyurethane.

The known epoxy resins contain repeating units of the formula

- O - CHg - CH

Examples of single epoxy resins are polyglyoidyl esters polybasic structures, as they are from the USA patent 2,866,767 are known to contain polyglyoid ethers of polyvalent Phenols, as described in U.S. Patents 2,467,171, 2,506,486, 2,640,037 and 2,841,595, and Polyglyoidyl Ethers of Polyhydric Alcohols, such as those in the United States patent 2 538 072 and 2 58I 464 are described. Usable curable polyesters contain, for example, a polymeric component (a) and a monomeric component (b), i.e. one or more methylene isoh unsaturated

1098-21 / 1898 SAD ORiGtNAL

polymerizable polyesters from polybasic. In particular Zwelbaslsohen carboxylic acids and polyvalent ones. In particular dihydric alcohols, and if necessary, residues of, for example, monobasic carboxylic acids, monohydric alcohols and Hydroxycarboxylic acids. where at least one of these radicals contains ethylenically unsaturated polymerizable groups, and one or more monomeric, ethylene-unsaturated,

contain
Connections that can be resolved Curable film compositions of this type are described in U.S. Patents 2,225,313 and 2,667,430. Modified polyesters of this type are described in U.S. Patents 2,628,209 and 3,219,604, for example.

Usable curable polyurethanes are for example in the U.S. Patents 2,721,811, 2,620,516, 3,061,497 and 3 105 062.

The wax-hardenable compound used for the central layer has at | a ratio of the thicknesses of the middle layer to the outer layers in the ratio of 1: 2 to 2t 1 two knots a viscosity in the area of. 200,000 to 1,000,000 ops, on the one hand not dealt too much squeezed from the mass and on the other hand a good one

- Pre-binding is achieved with the A-uBenlagen. In the preparation of

ο ■ ■

YYY moderately deep moldings made of comparatively thin composite » _ »Bodies according to the invention, however, the viscosity can also be - * be lower, while in the production of moldings,

· * Where the strength of the connection between the outer foils and the central position is not of essential importance,

jM- «av ·., : -» .. λ 8AD OHIGMAL

170UU

for example, because it is achieved by mechanical means, masses of higher viscosity can be used.
Means for controlling the viscosity of the heat-hardenable mass have already been mentioned above. The viscosity of polyesters can be increased, for example, by increasing the molecular weight of the polyester and / or changing its composition, for example by replacing a
Part or all of the styrene other monomeric compounds, such as acrylamide, diallyl phthalate, calcium acrylate, etc.,
used.

Fillers such as clay, asbestos, barite, ground silicon dioxide, magnesium carbenate, diatomaceous earth, etc .. can be used as an extender and / or to reduce the shrinkage of the mass during curing, which also increase the consistency of the mass. Oxides «Hydroxides or
Alkoxides of metals can, as known from the USA Patenteohrlft Z> 219 604, be used if moldings
which are exposed to relatively high loads,
should be produced. For example, the addition of magnesium oxide to a polyether makes a considerable amount
Increase in viscosity achieved. In addition, the thickening effect of magnesium oxide can. be controlled so that the
Increase in viscosity takes place gradually over the course of a few hours, which enables the mass to be deposited on an Olasfaeerbahn in a good flowable state. In this case

1098-21 / 1898

; -; mp SAO ORIGINAL

yti! iff! \ i! Tfffi ^^

- 17 -

can dl · Maes «by dipping the Oleafaaerbahn In dia ·· be brought in, while the Elndlokung d «r Maaea Ma mr Gawfiusohten viscosity «rat takes place when the middle position τοη the tharmoplaatieohan AuSenlagen is deoed. BaI the · «· Procedure will swleoban good wetting and good adhesion Olaafaaarmaterial and thermoplastic films enialt.

The thermoplastic fairs, which the Auöenfollen do

• Share, can reinforce »- or Arailerunganlttel, like a Wire mesh ^ included. Examples of theimoplaate that can be used are polyolefins »such as polyethylene, polypropylene and Miadipolyserlaate: and Terpolyaerlaate thereof, belaplelawelae Hlaohpolyaerisate of xethylene »and xthylaorylate, vinylpolynerlaate from belaplelawelae styrene «o-phenylatyrene, m-phenylatyrene, p-phenylstyrene, ο-methy! styrene, m-methyletyrene, p-methylatyrene, o-methoxyatyrene, n-ethoxystyrene, p-methoxyatyrene, ο-mitroateyrene, m-mitro-pyrene and p-nitrostyrenic phenyl- and vinyli- |

denhalogenlden, such as vinyl chloride, Vinylidenohlorld and Vinylldenbronld; Vinyl esters, such as vinyl acetate, vinyl propionate, Vinyl butyrate, vinylohloraoetat and Vlnylbansoati Polyoarbonate, i.e. thenaoplaatlaohe polymers with recurring Blnhelten the poreel

"0

Ji-

0 - Ar -

1098-21 / 1898

ßADOfilGJNAL

in Ar the remainder is a dihydric phenol let; Cellulose derivatives such as cellulose acetate, cellulose triacetate, cellulose acetate butyrate, cellulose proponate, and ethyloellulose; Polyamides, such as nylon 66, nylon 6, nylon 610, poly-n-xylylene, polyadipic acid amide and polyhexamethylene terephthalic acid amdj polyesters, such as polyethylene terephthalate, polyethylene isophthalate, poly (ethylene-2,7-naphthalate), poly (ethyl © np, p ^f - Dlphenylat) and spilled copolymers thereof in chlorinated polyethylene, chlorinated polyvinyl chloride, polyfluorolcohlenstoffe, such as polytetrafluoroethylene, polytrlfluorohlorMthylen, polyhexafluoropropylene and spilled copolymers and terpolymers thereof, such as copolymers of vinylidene fluoride and chlorinated vinylidene. Particularly good composite bodies according to the invention are obtained with polycarbonates, polyvinyl chloride, polysulfones, cellulose acetate butyrate, chlorinated polyvinyl chloride and chlorinated polyethylene.

When objects are of relatively great depth, for example When deep loops are to be produced, it is advantageous to use thermoplastic polymers with modlslerter Use SohlagsKhlgkelt below. When using such thermoplastic polymers with improved sole flexibility can auoh one; without any working deformation device used and thus a higher · production speed to be rewarded.

10 9 8-21 / 1898

BATH ORIGINAL

The impact strength can be increased in a known manner in an ohemieohem way by adding certain modifying agents. Bin increasing the impact resistance but can AUOH duroh a meohanisohe treatment of pollen, for example duroh cold or hot rolling or blaxlales drawing In the KKIte or Hltze _/ obtained, wherein duroh a solohe mechanical treatment AUOH the OleiohmäQlgkelt the thickness of the finished article can be improved.

Some synthetic plastics cannot be permanently deformed in the cold because of their elasticity, so that a molded body produced at normal temperature from a composite body according to the invention has a low dimensional accuracy after its removal from the die. This conclusion is usually referred to as "RÜokap ringen"("sprlngbaok"). Hence, it is twofold to wound thermoplastic pollen with poor "elastic memory". Bs has been found that · many amorphous polymers with 01asUbergan £ 8 ä temper at uranium can be permanently vorforat above room temperature in the cold. In addition, polymers can with a strong ^"0 RUokaprlngen be modified by that it is combined with non-elastic components, such as Netallfolien, networks, etc., examples of combinations are solohe pollen from an aluminum mesh reinforced polyethylene, from Kylon on a metal foil, etc.

As a means of improving the connection between the

109821/1898

BAD ORlGiNAt

17044U

thermoplastic adhesive films and the middle layer can be a Sohioht of short fibers between the middle layer and the thermoplastic pollen can be arranged.

Instead of using a fiber material between the middle layer and the thermoplastic outer foils can, if necessary, the adhesion between the middle layer and the outer foils but also through other means, for example through the use of adhesives or surface-active agents Funds are improved.

According to the method of the invention bcw. with the 'composite body According to the invention, moldings with certain requirements can be achieved Properties such as good impact strength at normal and low temperatures, high elasticity modulus at normal: and elevated temperatures, chemical resistance, l / ittering unstable. Heat resistance and dimensional accuracy, Abrasion resistance, favorable ratio of strength to weight, controlled permeability, good flammability, certain electrical properties and certain decorative effects can be produced.

The hardening of the middle layer after the deformation of the Composite body occurs either with normal or with elevated temperature Jedooh under the heat distortion temperature

1098-21 / 1898

· ^, 'ÜAt;

170UU

of the non-hardened molding ”. This temperature is usually close to the Olas transition temperature thermoplastic films. Hardening can also be done by induction * heat or electron beams or, if in the Middle layer a suitable metal powder dl aper giert 1st, duroh dielectrlaohea heating achieved «earth. Maintaining temperature and «For the time being from the thermosetting baron Nasse und Art and amount of catalyst present therein.

When using a polyester middle layer and linings from polyvinyl chloride, the UbIlohen peroxides can be used as Beard catalyst can be used. When using Bpoxyharsen together bit thermoplastic pollen from poly « carbonates or phenoxy hareses can be boron fluoride or tertiary amines can be used. Alternatively, an encapsulated Catalyst can be used, whereby the capsules tear during the deformation.

For the middle position, a vemetshares becomes two-pronged, initially thermoplasti8ob.es material that can be stored well and bsw. or has a long pot life at normal temperature. If it is not, the networking in a lot course time, this can also be done with normal Temperature duroh suitable activation of the resin, for example by subjecting them to radiation of high energy, for example sheet metal radiation, 8-radiation, ^ -radiation,

109821/1898

SADOfHGlNJM-

170U44

X-rays, ultraviolet light, etc. ^. The dosage of radiation depends on the composition the hardenable mass, its dloke, the penetration valve radiation, etc. Radiation curing is usually carried out at normal temperature and can be continuous be carried out "by" leading along the shaped body on a conveyor belt along the radiation source total volume of radiation is exposed. With such a process, very high productivity levels can be achieved. can be achieved.

After the middle layer has hardened, the finished molded body has often also at temperatures considerably above the Olas transition temperature the thermoplastic material of the outer foils has good dimensional accuracy.

The following examples are intended to illustrate the invention in more detail. Parts are by weight unless otherwise specified.

example 1

This example illustrates the production of shaped bodies from a composite body that consists of a central layer Made of fiberglass-reinforced polyester and rolled on two biaxially Polyvinylohlorldfollen is made. For a deformation according to the technique described above, the following is suitable

109 821/1898

- 25 -

Composition: Polyvinyl chloride Two polyvinyl chloride films from

60 parts each 0.038 in thickness

Glass fiber fabric 20 parts

Alliweokoplyester medium
Viscosity, expressed in 40 parts of styrene and 0.015 percent

Kobaltootoat * activates 20 parts Methyl ethyl ketone peroxide 0.2 parts

³¹ Also commercially available as "Plaakon PS-251" High Polyesters from Alled Chenloal Corporation can be used.

The fiberglass fabric was impregnated with the polyester mass

and on both sides with a biaxial thickness of 0.064 on Polyvinyl chloride rolled to a thickness of 0.038 on

foil covered. A circular a

Sample with a diameter of 9 on cut out and

immediately placed on the surface of the matrix and su one cylindrical bowl with a flat bottom of 5 on Durohmesser and 1.5 on wall height deformed.

The deformed composite body was taken out of the press and Allowed to cure for 24 hours at room temperature. Of the fortige color bodies had the following properties

1098-21 / 1898

. , BAD ORIGINAL

170A4A4

- 24 (determined at the bottom of the bowl) t

Tensile module *? 1 000 kg / on ² Flie »tension * 1 070 kg / om ² Thermal deformation temperature

"The tensile properties were measured in accordance with * 0 ¹¹ ASTM Standard Plastics Method of Testing, Part 27" June 1965 "D-1708".

³ ^ ⁸ The dimensional accuracy of fora bodies at elevated temperature was determined in a hot-air oven, which enabled an almost constant temperature rise of 2 * C /) 4 minutes. The temperature at which the upper durometer of the bowl expands by five pounds from its original diameter is measured as the water temperature.

A shell of the same dimensions made by Vergleloh from polyvinylchloride alone had a heat dissipation temperature of TCK, determined by the same process.

Example 2

This example illustrates the production of a molded body from a composite body from a Glass safes were impregnated with the penniless of polyester and two consists of biaxially rolled-out polyvinyl chloride films. The following composition is suitable for deformation according to the technique described above:

1098-21 / 1898
8AD ORIGINAL

170U44

Two polyvinyl chloride sheets from

j «0.046 om Dioke 65 parts

(!! • «fiber fabric 20 parts

All-sweat polyester of medium viscosity, dissolved in 40 parts of styrene and 0.015 part of cobalt octoate activated * 20 parts

Methyl ethyl ketone peroxide 0.2 parts

¹¹ AuOh Plaskon PE-251 can be used.

The manufacture of the composite body and its deformation were carried out as described in Example 1, with the difference that the polyvinyl chloride films contribute biaxially in light air 110% voa an initial locomotive of 0.76 om to a dioke of 0.046 om were rolled.

The fully cured shell had the following properties, determined as in Example 1;

Tensile module

Flow tension Heat forming temperature

29 400 kg / om '1 120 kg / cm ² 7OU

Example 3 This example illustrates how to make a Pormkkörperere made of a composite body, which consists of a

1098 * 21/1898

8AQ ORfQiNAL

The middle layer consists of glass fiber reinforced polyester and two biaxially rolled-on polycarbonate foils ³¹ :

Two polycarbonate sheets from

Each 0.046 cm Dioke 58 parts

Glass fiber fabric 24 parts

All-two polyester medium viscose *

eitMt. dissolved in 40 parts of styrene and

with 0.015 parts cobalt toottoat **

activates 18 parts

Methyl ethyl ketone peroxide 0.18 parts

^Mu h9X9n "of the General Bleotrio Company ¹⁰¹ AuOh Plaekon PE-251 fc * nn can be used.

The manufacture of the composite body and its deformation were carried out as shown in Example 1.

The polycarbonate sheets were biaxial from an initial dioke from 0.76 om to a thickness of 0.046 cm.

The fully cured sohale had the following Properties, determined as in example 1: Tensile modulus 31 500 kg / cm Tire strength 1 545 kg / cm ² Heat deflection temperature 1605;

1098-21 / 1898 8AD ORIGINAL

170U44

The shell is made entirely of polycarbonate Dimensions had a temperature of 140%.

Belaplel 4

This «example illustrates the production of forum doors made of composite bodies, which consist of a middle layer made of glass fiber reinforced epoxy resin and iwel pollen made of ohlorlerteot Polyethylene old 66 Oew.-ji chlorine consists of:

Two foils made of ohlorlertem polyethylene, each 0.04 on Dloke 62 parts

Glass fiber fabric 15 parts All-week epoxyhars made from bisphenol A.

of molecular weight JÖO, catalyzed

and networked old 10 Oew.-J * Diethylen-

trlaaln »17.7 parts

^N Auoh Bpon 828 of the Shell, catalyzes bit 10 to 12 oew.-jf diethylenetriaain. can be used.

The fundamental molar viscosity of the chlorinated poly-methylene was > .0, determined in o-dichlorobenzene at 100 ° C. The foils were biaxially rolled out to a diameter of 0.05 to 0.04 inches.

The manufacture of the composite body and its deformation as described in Example 1. After curing the Sohale had the following properties »

1098-21 / 1898

SAO ORIGINAL

- 28 determined as in example 1:

Tensile module 30 800 kg / cm ² Strength 1 330 kg / around ⁸ Wgrne deformation temperature 120T

Example 5

This example illustrates the manufacture of font bodies from a composite body made up of two foils Cellulose acetate butyrate and a middle layer made of glass fiber reinforced epoxy resin> whereby each of the two Orenzf laughs between a foil and the middle layer one Has a layer of short fibers, which sing partly into the middle layer and partly into the thermoplastic film beds are:

Two sheets of cellulose acetate butyrate, each 0.075 µm thick, 68 parts

Glass fiber fabric 15 parts Allzwackepoxyhars based on bis

phenol A with a molecular weight of 380

and catalyzed and networked _

with 10 ow. · * DiMthylentriaajin "20 parts

"Also Epon 628, catalyzed with 10 to 12 Gewr * difcthylen · triamine, can be used.

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In order to improve the bond between the pollen and the middle layer after hardening, a cotton fabric was pressed onto a surface of the pollen at 15 ° C. Then looker-bound cotton fibers were brushed off with a steel brush. In this way, a large number of course fibers were partly embedded in the surface of the foils, while in some cases they extended outward from the surface. Di ···. Foils were applied to the fiberglass-reinforced fiberglass wall in such a way that the fawn surface could come into contact.

Am "from these" composite bodies, as described in Chapter 1, produced Sohale had the following leagues "

Addition module 16 800 kg / o « ⁸ Tensile strength 9 800 kg / oe ²

heat deformation temperature 16OT

The heat loss temperature of the same but only made of cellulose acetate butterscotch kwetehendeji 8chale is about 30 *.

The ···· example illustrates the · production of font bodies from a composite body made of * wel acrylonitrile /

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ButadlenAfeyrolfollen on a central layer made of glass fiber

The strongest bpoxy resin consists of:

Two foils made of aorylnltrile / butadiene / Styrene, each 0.05 µm thick, 59 parts Glass fiber fabric 18 parts All-two epoxyhars based Bisphenol A of molecular weight

380 and catalyzed and networked:

with 10 Oew.-JfDlIthjrlenfcrlaBin * S £, 2 parts

* Auoh Bpon 828, With 10 to 12 Oew.-0 Diet hy lent riaein catalyzed, can be used «ground.

Between the two thermoplastic sheets, the biaxial rolled out from a dloke of 0 * 075 to a dloke of 0.05 0 « were, became a sobioht from the old dee Bpo * yhara impregnated fiberglass fabric introduced. This composite body was shaped as described in Example 1. The completely Hardened Sohale had the following general adhesion

Tensile modulus fi3 600 kg / e ² Tensile strength 905 kg / oe ⁸

heat aging temperature 100Ϊ

Example 7

The ··· example verantohaulicht dl · making a

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Shaped body made of a composite body consisting of a central layer Made of glass fiber reinforced polyester and two polysulfone fibers exists t

Two foils made of polytulfone (Union Carbide 3500) of 0.063 each on Dloke 58 parts Glass fiber fabric 23 parts

All polyesters of medium viscosity, dissolved in 40 parts of styrene and 0.015 parts of cobalt ozone
activated ¹¹ 20 parts

Methyl Ethyl Ketone Peroqrd 0.8 parts Plaskon PI-251 can be used.

The two polysulfone foils were rolled out from a diameter of 0.10 on to a diameter of 0.063 on. The composite body became, as in BeispJJ. 1 described ^ a Γ. their shell is made, the after complete hardening the a

had the following liability

Access module 84 600 kg / oa ² tensile strenght Heating temperature 185%

1 0 9 8-2 1/1 θ 9 θ

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Belsplsl S

The composite body dleeet Beleplel · consisted of swel polyphenylene oxide follen and a middle layer made of glass fiber reinforced polyester:

Two polyphenylene oxide pollen

(General Eleotrio) of ever

0.073 en plank · 61 parts

Glass fiber fabric 21 parts

Dissolved Alltweokpolyester medium viscosity in 40 parts of styrene and activated with 0 ₄₀₁₅ * 22 parts parts Xobaltootoat

Ethyl ethyl ketone peroxide 0.22 parts

³¹ AuOh Plaskon PB-251 can be used.

The polyphonylene oxide foils were biaxial from a Dloke of 0.113 on rolled out to 0.069 cm. From the composite body a shell was formed as described in example 1, the naoh completely · «curing the following properties had

Tensile module 23 500 kg / on ² tensile strenght 910 kg / on ² WKrnedeformationsteiiperatur 90 *

10 9 821/1898

Example 9

In this example, a composite body was made from two foils «Us« ine «high molecular linear epoxy resin, made duroh ttasetsen of bisphenol A with epiohlorhydrin * and one Nittellsge made of glass fiber reinforced polyester used!

Two foils made from the epoxy resin from 0.055 each whether Dioke 50 part « Fiberglass fabric 28 parts

Allsweok polyester of medium viscosity, dissolved in 40 parts of styrene and 0.015 part of cobalt octoate activates 18 parts

Ethyl ethyl ketone peroxide 0.18 parts

"" Phenoxy "from Union Carbide Corporation.

The two foils were from a thickness of 0 * 075 on to %

the diameter of 0.055 oa rolled out. The composite body was as described in Example 1, deformed, and dl «obtained Shell natta neon complete «hardening the following Kigsnsohaftem

2u0sodul 26 300 kg / oe ²

Tensile strength 9 * 5 kg / oe ² WMmeverlOreungsteojperature 95%

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Example 10

This example veransdi aulloht the production of moldings from a composite body «with the deformation in more than one process stage» all at normal Temperature have been carried out.

The composite body consists of two biaxially rolled out Polyvinylohloridfollen and an intermediate layer made of glass fiber reinforced Polyester:

Polyvinyl chloride Thickness of the outer foil 1.25 om Dloke the inner film 1.75 om

non-woven Olasfasfasertuoh, Impregnated with a polyester with a viscosity of about 800,000 ops (amount of glass approx. 25% by weight) *

Dloke of the middle layer 1.5 om

750 of the All led Chemloal Corporation.

Sin kreiaföxwlges piece of 22.5 on diameter was made cut the composite body and slide over a matrix the in Figure 4 veransohauliohten placed and su a cylindrical Bowl with a flat bottom, 12.5 om in diameter and a wall height of 3.75 om. This is the first stage of the deformation process * In stage 2, a

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second die, the bottom profile of which has a radius of curvature of 9Λ ca, used, ao dat the bottom of the fohale is rounded. Stage 3 of the "process" is carried out with a "Inen stamp with a hemispherical profile. The finished molded body has a bottom, the dimensions of which correspond to those of the last punch, and straight cross winds. The Oeiaathühe is. 6.8 om. In this three-stage deformation process, a shaped body bit is practically everywhere the same wall thickness M

obtained, while with the remaining single-stage deformation, usually particularly along the curvature of the bottom, one considerable weakening of the wall occurs.

Example 11 In this example, a composite of liner:. rvel-

Layer made of alkyd polyester resin and swel polyvlnylohlorldfollen used. Curing is done by irradiating de 'Fon body with low-energy slectron radiation. deformation and curing take place at normal temperature outside the mold.

It became an Allsweetcalkylhars with a viscosity of about 800,000 ops used, the su a film of 0.05 cn Dloke was rolled out. T) Ie polyvinyl chloride films were from 0.063 cm thick to a dloke of 0.038 om biaxial rolled out. All the composite body became a circular shape Piece »tilt a Durohmenser of 8.8 om cut out

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and below a cylindrical shell with a flat bottom of 5 cm Durohmessor and a wall height of 1.5 cm. This Sohale was cured by means of S-radiation.

Example 12

77 Otw. «Parts of a relatively high molecular weight polyester resin from the average molecular weight 160,000 and the eXuresahl 12.5. made by implementing the following Components:

Propylene glycol 1.05 moles Phthalic anhydride 0.5 mol Maleln's cure anhydride 0.5 mole Olympics 0.01 mole

were mixed with 23 parts by weight of styrene and 8 parts by weight of polyvinyl alcohol. The mass obtained had a viscosity of 800,000 ops. It was sprayed onto an advancing Olas mat by means of a T-shaped extrusion head, and was coated with a similar Qetowlndlndlkkelt, which the impregnated mat contained 50 Oew.-J * glass. Three layers of an Olas mat impregnated in this way were placed alternately as well as polyvinyl chloride foils on a smooth layer

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• 37 0.15 on.

This composite body is deformed into a bowl of 12.5 durohm with a flat bottom, as described above. Curing takes place with 3 radiation in a dosage of 5 megarads by means of a "Dynamitron Accelerator ¹¹ from Radiation Dynamios Ino." Using a voltage of 1,500,000 volts. G

Example 13 For this example, a composite was made from a

Resin-impregnated fiberglass mat as in Example 12 and svei

PolyvinylohloridfoUen made of the same thickness, its oesaatdioke

0.075 cm, while the median lago was 0.075 on diok wa * / *

The shell made as described in Example 12

was with X-rays (WK χ) at 55 IcV, 45 mA at a

Distance of the radiation source from the sample of 7.5 approx

cured for a total of 7 minutes. This Dosage ™ was sufficient for the hardening of the middle layer.

Example 1"

77 Oew. “Parts of a high molecular weight polyester are old average molecular weight of 16o,000 and an acid steel of 12.5, produced duroh tfasitien the following component ™

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Propylene glycol 1.05 MdI Phthalic anhydride 0.5 mol Maleic anhydride 0.5 hol Qlyoerin 0 * 01 MoX

are with 8 parts by weight of polyvinyl alcohol and 33 0 · «.- parts Styrene, of which 1 part by weight of bensoyl peroxide is used as a catalyst gugemisoht Ut, veraiaoht. The "preserved mate", the one Viscosity of about 800,000 ops ha ^ is on a · fortaohreitende Olaafaaernatte extruded, so that the impregnated Matt · 30 Oew.-j < 01a · reveals. Three Sohiohttn from di «s« r impregnated Olaamatte are superimposed and with two polycarbonate foils covered. From this composite body becomes, as described above, a Sohale through Yiefslehen manufactured. The sohale is hardened by heating it to 100% for 15 minutes. That happens. By controlling them * nuierlioh passes through an oven after it is removed from the molding device, as veranaohaulioht in Figure 6,

Example IS

70 parts by weight of an all-sweat polyester of medium viscosity, produced by tfasetsen the following components ι

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Propylene glycol 1 * 0 $ mol Phthalic anhydride 0.5 mol Maleic anhydride. 0.5 moles

old are 30 parts by weight of styrene and 1 part by weight of cobalt naphthanate wrongly. Just before the crowd hits the 01a - If it is applied to a matt finish, your 3 Oew.-parts of MethyIKthyI-ketone peroxide sugesetst as a catalyst.

The mass was spread on a glass fiber mat and
the semi-crystallized solution was wiped off one part with a squeegee so that the coated mass contained 30 owls. The mass was then placed in the form of swel polyvinyl chloride films and allowed to lean at a low temperature until the desired viscosity (about 600,000 opa) was reached. At this point the composite became cold / drained as described above.

Example 16

The composite of this example consisted of: swel
Cellulose triacetate follsn and a middle layer
fiberglass "polyether"

Two cellulose triacetate foils from

0.05 approx Dioke 35 ow parts each

Glass fiber fabric 83 oew parts Polyeattnaaaee 43 parts by weight

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The polyester mass had the composition given in Example 1 and, as described in Example 1, was incorporated into the glass fiber fabric. The deformation was also carried out as in Example 1 beaohrleben, and the shell was ph. cured for hours at room temperature.

Example 17

A composite like that of Example 16 using Jedooh one of the cellulose triacetate films contained a polyvinyl chloride film containing gleloher dioke, as described in Example 16, deformed and hardened.

Example 18

The composite of this example consisted of two thermoplastic Pollen from a high molecular weight linear epoxy resin made by unsets of dicumylphen-jl

with eplorohydrin, hereinafter referred to as cumoxy, and a middle layer made of fiberglass-reinforced polyurethane

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Two cumoxy sheets of 0.063 cm each Dioke 63 parts Olaa fiber fabric 22 oew. Parts Polyurethane 2h oew parts The polyurethane was made by reacting a polyether with the Bydroxylsahl 443 obtained with toluylene diisooyanate. 100 parts Polyethers were placed in a flask with an old stirrer and vacuum

built-in laser tube. The temperature of the polyether was raised with stirring to 75 m ^, and this temperature was maintained for 30 minutes, "while the polyether under a"

Vacuum of 3 to 10 mm Hg was degassed. After that, the PolyMther cooled to 5 <H, and 68.8 parts of toluene diisocyanate

oyanate were sugesetst. Then nooh was taking 5 minutes

Degassed stirring. After that, a fiberglass fabric was made with this Impregnated mass and covered with swel polycarbonate filings. This composite was as described in Example 1 ^

vtrformed, and the shell was cured for 4 hours at 100%.

example

The composite of this example consisted of two Mylon 6 foils reinforced with aluminum foil and a «· glass fiber reinforced polyurethane middle layer

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Aluminum - Hylon 6, two pollen

each 0.088 cm Dioke 35 (bold parts

Glass fiber fabric 25 Oew.-Telld Polyurethane. 25 ow parts

The Alurainiua / toylon-6 poles were made by a nylon 6 polie of 0.07 on DIoIm on an aluminum foil of 0.2 om plank. The urethane compound had the same composition as that of Example 18. BeIa Joining the three layers together were the Hylon foils of the Central position facing. The, as described in Example 1, Porn body obtained was cured at 100% for four hours.

JBelsplel 20

The procedure of example k was repeated, but instead of the pollen made from chlorinated polyethylene, other thermoplastic pollen were used »

by O.OO8 oa Dioke Ia experiment a) were Polylthylenfolien / in a Stahlnets (wire dioke 0.05 on «10 aesh per linear inoh) • Was stored, used.

In experiment b), polyethylene foils of 0.063 om Dioke, in dl "in aluminum net" (wire dioke 0.025 cm, 60 mesh per linear Inoh) stored uar, used.

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In experiment ο) polyethylene films of 0.0 $ on Dioke, in which an aluminum foil from 0 * 013 on Dioke was embedded «was used.

In any case, the net was stored in the polyethylene filament been stored, inden "heated to the Polyäfchylenfolle and suseamen old the metal net or the metal" The film passed between two pressure rollers, so that ^

the polyethylene, heated to about 190 ° C, is bound to the metal became. The pollen thus produced was applied to an epoxy resin middle layer. Cold-formed moldings from these composite bodies "showed no fluffy" backlash ", i.e. they retained their shape so that they could be cured.

Example 21 The procedure of Example 20 «part a) and o) was repeated

with the deviation that for the thermoplastic-like foils * instead of polyethylene polypropylene gleloher Dioke was used *

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Claims (11)

Claims ί · Can be deformed into shaped bodies «Composite bodies, which are a after deformation hardenable resin contain «characterized that they come from a central position (15, 20, 25) of a thermosetting mass and on both sides thereof at least one layer (16 «17 * 21, 22,26,27,28) of one thermoplastic plastic mass exist. 2. Composite body according to claim 1, characterized in that the outer layers are made from different thermoplastic materials Plastics. 3. Composite body naoh claim 1 or 2, characterized in that that the middle layer contains a polyester, a polyurethane or an epoxy resin. 4. Composite body naoh claim 1, 2 «of 3, daduroh characterized, that the middle layer is reinforced with Olasfasematerial eats. 5. Composite body naoh claims 1, 2, 3 or 4, daduroh 1 0 9 8 · 2 1/1 8 9 · 8AD OWGINAL 170UU marked that the thermoplastic outer layers are durable • are reinforced in metal wire mesh or a metal foil. 6. A process for the production of porous bodies *, characterized in that a composite body according to one of the preceding claims is deformed in the desired manner and the molded body is then cured free of external delimitation. M. 7. Procedure according to Claim 6, «thereby knowing» that the middle layer is hardened »by» to the body of the body to a temperature below the Wäraeverformungstemptratur the thermoplastic layers are heated. 8. The method according to claim 6 or 7 * daduroh gekennjtelohnet, that the composite body is produced by using a Sheet (41,87) of the thermosetting material continuously, mix sheets of the theraoplastic material (48.89 * 90) ' arranges. 9. The method according to claim 8, characterized daduroh that one sheet of Fasenoaterlal in the thermosetting Stores mass. 10. The method according to claim 9 «daduroh gekennselohnet that the web of fiber material (4l) is impregnated by 1 098 * 2 1/1 89 SAD ORJGiNAt 170AAAA - 46 - ei · leads through a the warmth * rtend · Mo ·· containing ·· B «d, before nan applies the thermoplastic strips (4S). 11. The method according to claim 10, characterized in * da3 the sheet of paeno material (4l) during its passage is carried through the bath (42) by a «conveyor belt (46). 109821/1891 8AD ORIGINAL